Organo manganese compounds and method of making same



hydrocarbon radicals having up to .the organoyl radical has up to 13carbon pentacarbon'yls is incorporated forth.

them in liquid form, as

-diethyl ether, diethylene glycol monoethyl'ether,

United States PatentO 3,081,324 ORGAN MANGANESE COMPOUNDS AND METHOD OFMAKING SAME --Kestutis A. -Keblys,.West Lafayette, Ind., assignortoEthyl Corporation, New York, ginia i No Drawing. Filed Jan. 18,1960,'Ser. N.o. 2,825 19. Claims. (Cl. 260-429) N.Y., a corporation ofVir- =Thisinventi0n relates to organic compounds of manganese, moreparticularly to such compounds in which a pluralityrof carbonyl groupsis present. This invention further relates to methods of making andusing these compounds.

Among the ObjGCiZS of the present invention is the provision of novelcompounds of the above type which are simple to form and which havedesirable uses.

The above as Well as additional objects or the present invention will bemore fully understood from the following description of several of itsexemplifieations.

The compounds of the present invention are organoyl manganesetetra'carbonyl ammonias in which not more than two of the ammoniahydrogens are substituted by 13 carbons each, and

atoms.

These compounds are very conveniently formed by merely mixing ahydrocarbyl manganese pentacarbonyl With an ammonia corresponding to theone desired in the final compound. The' hydrocarbyl manganesepentacarbonylsas Well as methods for making. them aredescribed in US.Patent 2,9l3,4l3. granted November 17, 1959, and the pertinentdisclosures of the preparation of these herein as though fully setAlthough compounds of the present invention can have more than 13carbons in any of thehydrocarbon radicals substituted'for the ammoniahydrogen as well as in the organoyl radical, the use of more than 13carbons in any one groupie not preferred. The organoyl radicals can" beof the acyl or aroyl types although those of the acyl type more readilyform the desired compounds, and the compounds thus formed react moresmoothly and efiiciently.

The'r'eactionthat forms the compounds of the present invention takesplace at room temperature as well as at temperatures as much as 70 aboveand below roomtemperature.

at temperatures of from about In the interest of simplicity, it is bestto operate 35 to 50 C. The manganese pentacarbonyls used as startingmaterial for producing the desired compounds are generally low meltingsolids and they are more efficiently" reacted by placing v by dissolvingthem ina suitable solvent or by melting them. Suitable solvents arehydrocarbons such as gasoline, iso-octane, petroleumether and n-dec'ane,others such as tetrahydrofura'ne, diethyl ether, dipropyl ether,ethylene glycol monomethyl ether, ethylene .glycol dimethyl ether,diethylene glycol monomethyl ether, diethylene glycol dimethylether,ethylenelglycol diethylene glycol dibutyl ether, ethanol,propanol, butanol, acetone, methylethyl ketone and methyl 'isobutylketone.

In general, all normally liquid hydrocarbons and normally liquid ethersand alcohols are effective for this purpose.

The reaction or" the ammonia with the hydrocarbyl manganesepentacarbonyl generally takes at least about /2 hour to go tocompletion. As a matter of precaution the reaction can be continued foras much as hours or more to assure good .yields in the event one of thereactants is in the solid phase, or contaminants slow down the reactionvelocity. The following examples, whereall parts are parts by weightunless qtherwise specified,show some otthe variations in thereactiontechnique:

.Mn, 1 7.9; N, 4,;3; mol. t, 295.

.with stirring for 2 hours.

.Mn, 17.4;.N, 4.44.

3,081,324 Patented Mar. 12, 1 963 "ice .2 EXAMPLE I .Cyclohexylamine"Acetylmanganese ,Tetracarbonyl The infrared spectrum (carbontetrachloride solution) showed bands at 4.8a, 495a, 5.05 and 5.15;. inthe metallo-carbonyl region and a ketonic carbonyl; band at Itsrnolecular weight wasdetcrmined cryoscopically, and it wassubjectedtoelemental analysis, with th fo win r u t Calculated for C12lI1 MHNO5ZC, 46.6; H, 5.21; Mn, 17.8;; .N,.4.53; mol wt, 309. Found: C, 46.6;H,5.37;

EXAMPLE II Ammonia Acctylmrmganese retrqcartronyl .A' mixture ofmethylmanganese pentacarbonyl (4.0 g., 0.019 mole) and liquid ammonia(200 ml.) was refluxed I Excess ammonia wasallowed to evaporate slowly.Agreenish-yellow solid (4.11 g., 95 percent) remained in the reactionvessel. Recrystallization from'diethyl ether gave 3.65 g. of ammoniaacetylmanganese tetracarbonylglight yellow crystals, melting at95-;596.0 C. with decomposition.

Arraly'sis.'Cal-culated for C H MnNO C,-'31.8; H, 2.69; Mn, 24.2;N,6.17. FOundZ C; 32.4; H, 2.70;

EXAMPLE III N-M ethylcyc lohexylamilre Acetylmanganese T etracarbonyl y1 Methylmanganese pentacarbonyl (5.0 g., 0.024 mole) andN-mcthylcyclohexylamine (4.0 g., 0.036 mole).were

dissolved in 50ml. of tetrahy-drofuranend' stirred "at room temperaturefor 2 hours. Excess solvent was evaporated in vacuo. .The residues werecooled. in Dry I Ice giving 3.1 g. (40%) of yellow crystals.' Theproduct,

recrystallized from petroleum ether (B.P. 38-42" C.), meltedat.73-.74.C.

Analysis.-Calculated for C H MnNo C, 48.3; H, 5.60; Mn, 17.0; N. 4.33..Found! C, 48.3;v I-I,- 5.58;

EXAMPLE I V Aniline Acetylmqrtgartese Tetracarbonyl Methylrnanganesepentacarbonyl (3.0 g., 0.014 mole.) and anil ne (2.0 g., 0.022 mole)were dissolved in 50 ml. of tetrahydrofuran andv kept under nitrogen atroom temperature for hours. 'l'hen the solution was poured into 400 ml.of ice water, giving a yellow precipitate, which after washing and,drying weighed 1.72 g- (38%).

Recrystallization from ether gave yellow crystals, melting at s3-s4 c.

Analysis.Calculated for C H MnNo C,- 47.6; H, 33.3; Mn, 18.1; N, 4.62.'Found: vC, 46.6; H,.33.3; Mn, 17.8; N, 4.70.

EXAMPLE V Cyclohexylamine Benzoylmanganese Tctrqcarbonyl Phenylmanganesepentacarbonyl (2.0 g., 0.0074 mole) and cyclohenylarnine(0.80 g., 0.0081mole) were'dissolved a in 35 ml. of diethyl ether and stirred at roomtemperature for 1.5 hours. The resulting orange solution was cooled inDry Ice giving 0.25 g. (12% recovery) of phenylmanganese pentacarbonyl.The mother liquor was concentrated, cooled in Dry Ice and filtered,giving 0.87 g. of an orange, heterogeneous, solid mass and anorange-brown viscous filtrate. The filtrate was dried over potassiumhydroxide pellets and parafiin flakes, giving 0.70 g. of a tacky, brownsolid. Repeated extraction of this with petroleum ether, concentrationof extracts, and cooling gave 0.23 g. yield) of crude cyclohexylaminebenzoylmanganese tetracarbonyl. Recrystallization from petroleum ethergave a yellow solid, melting at 7578 C.

EXAMPLE VI Aniline Benozylmanganese T etracarbonyl Phenylmanganesepentacarbonyl (2.72 g., 0.010 mole) and anilfne (1.02 g., 0.011 mole)were dissolved in 30 ml. of ether and allowed to stand at roomtemperature under nitrogen for 163 hours. The resulting yellowbrownsolution was filtered and cooled in Dry Ice giving 0.83 g. of yellowcrystals. Fractional crystallization from petroleum ether gave 0.22 g.of benzoylmanganese pentacarbonyl and 0.61 g. of starting material. Themother liquor was concentrated and cooled giving 0.50 g. of startingmaterial (total recovery of 41%). After further concentration the motherliquor was treated with iso-octane precipitating a dark yellow solid(0.23 g., 10%). The crude product melted at 7879 C.

By way of comparison neither trimethylamine nor pyridine could be madeto react with the hydrocarbyl manganese pentacarbonyls to form thedesired products.

The above formation reactions do not require the presence of anymaterials other than the reactants, and no special treatment is neededas long as these reactants are caused to contact each other. After about/2 hour of such contact even at temperatures as low as 40 C., arecoverable yield of product is obtained. Reaction tem peratures above100 C. are not desirable because the desired products tend to decomposeat these temperatures, patricularly when in concentrated form. Theseproducts are generally low melting crystalline solids with fairly strongcolor, very slightly soluble in petroleum ether, cold iso-octane andcold methanol when the ammonias range up to di-tridecyl amine,omega-phenyl amylamine, 4-hexyl-cyclohexyl amine and beta-heptylpiperidine. Other ammonias that are suitable for the purposes of thepresent invention include methylamine, ethylamine, dipropylamine,cyclopentylamine, amino cyclohexadiene- 2,4, allyl amine, naphthylamine,N-tetrahydroquinoline, and pyrimidine. Ammonia itself andaliphatic-substituted ammonias react most rapidly to form the desiredcompounds.

The hydrocarbyl groups in the original manganese pentacarbonyl can rangeup to 12 carbons in size and preferably are alkyl groups inasmuch as theyields are much lower with aryl groups. Good results can be obtainedwith hydrocarbyl groups such as phenyl, toluyl, xylyl, dodecyl,para-dicyclohexyl, hexyl pentyl, butyl and vinyl. As a result of thereaction, the hydrocarbyl groups have a carbonyl group added and areaccordingly converted to hydrocarboyl groups with one additional carbon.

The hydrocarboyl manganese tetracarbonyl ammonias of the presentinvention are cleaved by strong alkali such as sodium methylate to splitoff the hydrocarboyl portion from the balance of the molecule. Themethylate of the hydrocarboyl group is thus formed, corresponding to themethyl ester of the carboxylic acid that has an OH group connected tothe hydrocarboyl group. With other alcoholates, the corresponding otheresters of the same acid are formed. With sodium hydroxide theunesterified acid is formed.

The remainder of the split molecule appears to be an ammonia complexNaMn(CO).,-ammonia. -When treated with methyl iodide this remainderdisproportionates to give methyl manganese pentacarbonyl along withbisammonia iodomanganese tricarbonyl.

The above cleavage reactions establish the structure of the originalhydrocarboyl manganese tetracarbonyl ammonias and show that in theformation of these compounds one of the carbonyl groups of thepentacarbonyl reatcant becomes linked to the hydrocarbyl radical. Thisshift is reversed in the presence of strong acid, and the hydrocarbylmanganese pentacarbonyl thus recovered along with the corresponding saltof the amine. Both their cleavage and the reversal of their formationreactions provide valuable uses for the compounds of the presentinvention.

The cleavage provides one simple technique for the direct formation ofesters from hydrocarbon halides or sulfates. These starting materialsreadily react with NaMn(CO) as shown in Examples XXX and XXXI of US.Patent 2,913,413, to give the hydrocarboyl manganese pentacarbonyl usedas a reactant to form a hydrocarboyl ammonia of the present invention.Although that Example XXXI describes the reaction of a hydrocarboylhalide with the above sodium compound, hydrocarbyl halides react in thesame way although less vigorously. The hydrocarboyl ammonia can then becleaved with or without prior purification, to form the desired ester.Any other alkali metal salt of a hydroxy hydrocarbon can be used in thecleavage, as for instance sodium ethylate, lithium beta phenyl ethylate,potassium cyclohexylate, rubidium octadecylate, etc. The following is atypical cleavage run:

EXAMPLE VII Cleavage of Cyclohexylamine Acetylamarzganese TetracarbonylWith Sodium Melhoxide To the cyclohexyalmine acetyl manganesetetracarbonyl of Example I (10.0 g., 0.032 mole) dissolved in 300 ml. ofmethanol there was added dropwise a solution of sodium methoxide (1.75g., 0.032 mole) with ice cooling. After the addition the solution wasstirred at room temperature for 2.5 hours. Approximately ml. of solventwas distilled otf and the fraction boiling in the range of 53.2-63.9 C.was identical to an authentic methanolmethylacetate azeotrope.Refractive index data showed that the product contained 1.6 g. ofmethylacetate (69% of theory).

Twelve milliliters of the azeotrope was refluxed with 4 ml. ofbenzylamine and 0.1 g. of ammonium chloride for 42 hours. Methanol wasthen distilled off, and the residue neutralized with aqueous HCl. Etherextraction and evaporation gave white crystals which melted at 63-64 C.after recrystallization from n-hexane-ether. No melt'ng point depressionwas observed with an authentic sample of N-benzylacetamide.

The ammonia fraction of the cleavage remained in the reaction mixtureafter the first distillation and was treated with methyl iodide (13.6g., 0.096 mole) and stirred at room temperature for 2.5 hours. Thesolvent was evaporated in vacuo, leaving 60 ml. of a brown solution.Methyl manganese pentacarbonyl (0.48 g.) sublimed out of the reactionmixture during the evaporation. Yellow-brown flakes ofbis-cyclohexylamine iodomanganese tricarbonyl crystallized out of thebrown solution after standing overnight. After recrystallization fromchloroform the solid melted at 192.0192.5 C. with decomposition.

Analysis.Calculated for-C H IMnN O C, 38.8; H, 5.65; I, 27.4; Mn, 11.9;N, 6.04. Found: C, 39.3; H, 5.89; I, 27.9; Mn, 11.6; N, 6.03.

Similar cleavages produce hexadecyl octanoate, 4-phenyl cyclohexylbenzoate, beta naphthyl heptanoate. By selecting non-azeotropic cleavagesolvents or even using non-azeotropic diluents that are not solvents forthe cleavage reactants, the distillation of the ester is simplified.

The hydrocarboyl manganese tetracarbonyl ammonias of the presentinvention are also good gasoline additives since they produce efiectiveoctane rating increases notwithstanding their low solubility in thegasoline. At a concentration of 1 pound per thousand barrels anilineacetylmanganese tetracarbonyl will by way of example substantially raisethe octane rating of unleaded 100 octane gasoline, and will also producea substantial increase in the octane rating of gasoline containing 3 cc.of tetraethyllead per gallon and having an octane rating of 96.

In the formation of the hydrocarboyl manganese tetracarbonyl ammonias itis not necessary to use a nitrogen atmosphere. The reaction atmospherecan be ordinary air without changing the results.

Obviously many modifications and variations of the present invention arepossible in the light of the above teachings. It is therefore to beunderstood that, within the scope of the appended claims, the inventionmay be practiced otherwise than as specifically described.

What is claimed is:

1. Compounds selected from the class consisting of hydrocar-boylmanganese tetracarbonyl ammonia compounds, hydrocarboyl manganesetetracarbonyl primary amine compounds, and hydrocarboyl manganesetetracarbonyl secondary amine compounds wherein the hydrocarboyl radicalis an acyl radical having up to about 13 carbon atoms derived from acarboxylic acid, and is selected from the class consisting ofalkylcarbonyl, cycloalkylcanbonyl, alkarylcarbonyl, arylcarbonyl, andaralkylcarbonyl radicals; and wherein the organic radicals in theprimary and secondary amine portions of the hydrocarboyl manganesetetracarbonyl primary and secondary amine compounds are hydrocarbonradicals having up to about 13 carbon atoms and are selected from theclass consisting of alkyl, cycloalkyl, cycloalkenyl, alkenyl, aryl andaralkyl radicals.

'2. The compounds of claim 1 where-in the hydrocarboyl radical is analkylcarbonyl radical.

3. The hydrocarboyl manganese tetracarbonyl am monia compounds of claim1.

4. Ammonia acetylmanganese tetracarbonyl.

5. The hydrocarboyl manganese tetracarbonyl primary amine compounds ofclaim 1 wherein the primary amine is cyclohexyl amine.

6. Cyclohexylamine acetylmanganese tetracarbonyl.

7. Cyclohexylamine benzoylmanganese tetracanbonyl.

8. The hydrocarboyl manganese tetracarbonyl primary amine compounds ofclaim 1 wherein the primary amine is aniline.

Aniline benzoylmanganese tetracarbonyl.

l0. Aniline acetylmanganese tetracarbonyl.

11. The hydrocarboyl manganese tetracarbonyl secondary amine compoundsof claim 1 wherein the secondary amine is N-methyl cyclohexylamine.

12. N-methylcyclohexylamine acetylmanganese tetracarbonyl.

13. Process for the preparation of the compounds of claim 1, saidprocess comprising reacting a compound selected from the classconsisting of ammonia and primary and secondary amines, wherein theorganic radicals of said primary and secondary amines are hydrocarbonradicals having up to about 13 carbon atoms and are selected fromtheclass consisting of alkyl, cycloalkyl, cycloalkenyl, aryl, alkenyl andaralkyl radicals; with a hydrocarbyl manganese pentacarbonyl in whichthe hydrocarbyl radical corresponds to the desired hydrocarboyl radicalwithout its carbonyl moiety.

14. Process for the preparation of cyclohexylamine acetylmanganesetetracarbonyl, said process comprising reacting methyl manganesepentacarbonyl with cyclohexylarnine.

15. Process for the preparation of ammonia acetylmanganesetetracarbonyl, said process comprising reacting ammonia with methylmanganese pentacarbonyl.

=16. Process for the formation of N-methyl cyclohexylamineacetylmanganese tetracarbonyl, said process comprising reactingmethylmanganese pentacarbonyl with N- methyl cyclohexylamine.

17. Process for the preparation of aniline benzoyl manganesetetracarbonyl, said process comprising reacting phenylmanganesepentacarbonyl with aniline.

18. Process for the preparation of cyclohexylamine benzoyl manganesetetracarbonyl, said process comprising reacting phenylmanganesepentacarbonyl with cyclohexylamine.

19. Process for the formation of aniline acetylman ganese tetracarbonyl,said process comprising reacting methylmanganese pentacarbonyl withaniline.

References Cited in the file of this patent UNITED STATES PATENTS1,459,971 Carter et al June 26, 1923 2,398,157 Ramage Apr. 9, 19462,818,416 Brown et al Dec. 31, 1957 2,913,413 Brown Nov. 17, 19592,927,935 Cofiield et a1. Mar. 8, 1960 2,930,807 Case Mar. 29, 1960 lFOREIGN PATENTS 1,201,531 France July 15, 1959-

1. COMPOUNDS SELECTED FROM THE CLASS CONSISTING OF HYDROCARBOYLMANGANESE TETRACARBONYL AMMONIA COMPOUNDS, HYDROCARBOYL MANGANESETETRACARBONYL PRIMARY AMINE COMPOUNDS, AND HYDROCARBOYL MANGANESETETRACARBONYL SECONDARY AMINE COMPOUNDS WHEREIN THE HYDROCARBOYL RADICALIS AN ACYL RADICAL HAVING UP TO ABOUT 13 CARBON ATOMS DERIVED FROM ACARBOXYLIC ACID, AND IS SELECTED FROM THE CLASS CONSISTING OFALKYLCARBONYL, CYCLOALKYLCARBONYL, ALKARYLCARBONYL, ARYLCARBONYL, ANDARALKYLCARBON RADICALS, AND WHEREIN THE ORGANIC RADICALS IN THE PRIMARYAND SECONDARY AMINE PORTIONS OF THE HYDROCARBOYL MANGANESE TETRACARBONYLPRIMARY AND SECONDARY AMINE COMPOUNDS ARE HYDROCARBON RADICALS HAVING UPTO ABOUT 13 CARBON ATOMS AND ARE SELECTED FROM THE CLASS CONSISTING OFALKYL, CYCLOALKYL, CYCLOALKENYL, ALKENYL, ARYL AND ARALKYL RADICALS.